CN104195495A - Oxide nanoparticle doped WO3 gas sensitive coating and preparation method thereof - Google Patents
Oxide nanoparticle doped WO3 gas sensitive coating and preparation method thereof Download PDFInfo
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- CN104195495A CN104195495A CN201410407285.0A CN201410407285A CN104195495A CN 104195495 A CN104195495 A CN 104195495A CN 201410407285 A CN201410407285 A CN 201410407285A CN 104195495 A CN104195495 A CN 104195495A
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Abstract
The invention discloses an oxide nanoparticle doped WO3 gas sensitive coating and a preparation method thereof. The oxide nanoparticle doped WO3 gas sensitive coating is prepared by the following steps: by using an oxide nanoparticle doped WC16 solution as a spraying raw material, spraying and precipitating the spraying raw material on a base body by virtue of a thermal spraying process to obtain the oxide nanoparticle doped WO3 gas sensitive coating with the grain size of 10-50nm, wherein the mass ratio of oxide nanoparticles to WC16 is 1:(5-100). The invention provides the preparation method of the oxide nanoparticle doped WO3 gas sensitive coating. The preparation method has the advantages of few process flows, low cost and the like, is simple to operate and suitable for industrialized production. The thickness range of the prepared gas sensitive coating is 200nm to 1 mu m. The gas sensitive layer has a porous structure, and the grain size of WO3 in the gas layer is 10-50nm, so that the requirement on the high specific surface area of the WO3 coating in the field of gas sensitive sensors can be satisfied, and thus the application of the coating in the field of gas sensors is facilitated.
Description
Technical field
The present invention relates to metal oxide semiconductor WO
3coating technology field, relates in particular to a kind of WO that utilizes oxide nano-particles doping prepared by hot-spraying techniques
3air-sensitive coating and preparation method thereof.
Background technology
Along with China's rapid economic development, a large amount of uses of industrial fossil oil and automobile cause NO
x, CO
x, SO
2, H
2s, NH
3deng gas purging, caused the pollution of air, cause acid rain and Greenhouse effect, people's health has been formed to certain harm simultaneously.In order better to monitor inflammable and explosive, the poisonous and hazardous gas of this class, need exploitation is highly sensitive, selectivity is good gas sensor and relevant device badly.The advantages such as Metal Oxide Semiconductor Gas Sensing sensor is due to its sensitivity and selectivity is high, cost is low, simple to operate, easy to carry have caused investigator's attention.
WO
3as a kind of transition metal oxide semiconductor material, be a kind of N-shaped semi-conductor of broad-band gap, there is good air-sensitive performance, to some gas (as O
3, NO
2, NO, NH
3, H
2s) there is good sensitivity characteristic and paid close attention to widely.In general, the factor that affects sensor gas-sensitive property mainly contains susceptibility, selectivity, stability, time of response and repeatability etc.Just how to improve transducer sensitivity, forefathers have studied discovery, improve WO
3the specific surface area of coating can significantly be improved its sensitivity, and this is because the higher specific surface area of coating can be medium-gas more attachment point is provided, and has increased the contact area of gas and air-sensitive coating.Nano material has special mechanics, calorifics, optics, chemistry and magnetic, compares with coating prepared by traditional micro materials, and it possesses larger specific surface area, and therefore, preparation has nano-scale WO
3the air-sensitive coating of crystal grain has larger performance advantage.
WO
3the preparation method that coating is traditional mainly contains vacuum vapor deposition, sputtering method, vapor phase growth sedimentation, epitaxial deposition method, laser deposition, sol-gel method, electrodip process, silk screen print method and hydrothermal method etc.Traditional preparation or complex process, apparatus expensive, or production cost is higher, unsuitable industrialization, or residual gas poisonous and harmful, or film size is little, film forming, or film forming matrix is on a large scale limited etc.Therefore, realize WO
3the large-scale production and application of coating, need the coat preparing technology of developing a kind of novel low cost, high quality, big area, being applicable to suitability for industrialized production badly.
Hot-spraying techniques is a kind of surface strengthening technology, is the important component part of surface engineering technology, is the sufacing that is applicable to industrialization, big area production.In addition, hot-spraying techniques also has some advantages of himself, as unrestricted in body material; The coated material that can spray is very extensive, and hot-spraying techniques can be used to spray nearly all solid engineering materials; In spraying process, body material heats up littlely, does not produce stress and distortion; Operating procedure is flexible, not limited by workpiece shape, easy construction; Coat-thickness a wider range of preparation; Coating performance is varied, can form the coating that wear-resisting, anti-corrosion, heat insulation, anti-oxidant, insulation, conduction, radioprotective etc. have various specific functions; Strong adaptability and the advantage such as good in economic efficiency.Wherein, plasma spraying technology is a kind of important hot-spraying techniques, is also a kind of effective nano coating technology of preparing; But due to features such as solid nano powder quality are light, mobility is poor, be not suitable for directly as plasma spraying raw material, when tradition is prepared nano coating, often follow the operational path of " preparation of nano raw material → mono-time agglomeration granulation → secondary densification granulation → coating ", this route technique is loaded down with trivial details, operability is poor, and each process nano-powder has loss in various degree.In addition, in secondary granulation process, because temperature is higher, nano-powder crystal grain often has the trend of growing up, and may exceed nanometer critical size, and then affects the various excellent properties of nano coating.
Liquid phase plasma spraying is to grow up on the basis of traditional plasma spraying, it makes original pressed powder feeding change liquid phase feeding into, liquid phase presoma or suspension liquid are carried out to coating preparation as spraying raw material, this technology unites two into one powder preparation and coating preparation, has simplified processing step; Because evaporation and the volatilization of liquid phase in spraying process can be taken away a large amount of heat, so that the temperature of particle experience is lower, avoided nanocrystal too to grow up.Liquid phase presoma plasma spraying mainly concentrates on nanometer zirconia heat barrier coating preparation field both at home and abroad at present, to WO
3the preparation of air-sensitive coating relates to less.Therefore, developing liquid phase presoma is the submicron vesicular structure WO that raw material is prepared a kind of low cost, industrialization, high sensitivity
3air-sensitive coating has important using value.
Summary of the invention
The invention provides a kind of WO of oxide nano-particles doping
3the preparation method of air-sensitive coating.By the doping of oxide nano-particles, significantly reduce WO in air-sensitive coating
3grain-size, improve WO
3the sensitivity of air-sensitive coating.That described preparation method has is simple to operate, technical process is few, cost is low, be applicable to the advantages such as suitability for industrialized production.
A kind of WO of oxide nano-particles doping
3the preparation method of air-sensitive coating, comprises the steps:
WCl with oxide nano-particles doping
6solution is as spraying raw material, through hot-spraying techniques, spraying raw material is spray deposited to matrix, obtains the WO of oxide nano-particles doping
3the grain-size air-sensitive coating that is 10～50nm;
Described oxide nano-particles and WCl
6mass ratio be 1:5～100.
In the present invention, the liquid phase presoma of preparation coating is carried out to coating preparation as spraying raw material, powder preparation and coating preparation are united two into one, avoided the loss in various degree of nano-powder in traditional hot-spraying techniques, also there will not be in traditional thermal spray process, but because temperature is higher, make nano-powder grain growth in coating preparation process even exceed nanometer critical size, and then affect the various excellent properties of nano coating.Therefore, the present invention further by doping oxide nanoparticle in spraying raw material, significantly reduces WO in air-sensitive coating again
3grain-size, and be controlled within the scope of 10～50nm, and then obtained the WO of air-sensitive performance excellence
3coating.
As preferably, described oxide nano-particles is aluminium sesquioxide nanoparticle or titanium dioxide nano-particle, and the particle diameter of aluminium sesquioxide nanoparticle is 20～60nm, and the particle diameter of titanium dioxide nano-particle is 5～30nm.
The preparation process of described spraying raw material is:
First by WCl
6join in dehydrated alcohol, fully, after reaction, add water and tensio-active agent, and regulate pH value to 7～8 with ammoniacal liquor, then add oxide nano-particles, after mixing, obtain spraying raw material;
WCl in described spraying raw material
6quality percentage composition be 4～10%, the quality percentage composition of tensio-active agent is 0.06～0.15%, the volume ratio of water and dehydrated alcohol is 1:1～4.
The mixing solutions of tensio-active agent, water and dehydrated alcohol, makes to spray WO oxide-doped in liquid material
3slurry disperses more even, is beneficial to spraying process and carries out smoothly.
As preferably, described tensio-active agent is at least one in polyoxyethylene glycol, cetyl trimethylammonium bromide, ammonium polyacrylate.
Further preferably, WCl in described spraying raw material
6quality percentage composition be 4%, the quality percentage composition of tensio-active agent is 0.06%, the volume ratio of water and dehydrated alcohol is 1:1;
Described oxide nano-particles and WCl
6mass ratio be 1:10～100;
Described tensio-active agent is polyoxyethylene glycol, can be at least one in PEG20000, PEG6000, PEG600.
The thermospray adopting in the present invention is plasma spraying, concrete technology parameter is: the electric current of plasma spraying is 550～650A, voltage is 45～60V, spraying raw material flow is 30～80ml/min, spray distance is 140～200mm, plasma gun translational speed is 300～600mm/s, and coating spraying pass is 10～30 times.
As preferably, the electric current of plasma spraying is 600A, and voltage is 55V, and spraying raw material flow is 50ml/min, and spray distance is that 170mm plasma gun translational speed is 300mm/s, and coating spraying pass is 15～30 times.
Matrix described in present method is aluminum oxide, No. 45 steel, 304 stainless steels, polished silicon slice or slide glasss.
For sensor, coat-thickness is not more thick better, and coating can effectively cover substrate surface; Oxide content is also not The more the better, and its addition reaches after certain proportion, owing to forming larger particle, is unfavorable on the contrary gas detection, need consider each side factor.The air-sensitive coating that adopts method of the present invention to prepare, its thickness range is 200nm～1 μ m, and possesses vesicular structure, WO in air-sensitive coating
3grain-size be 10～50nm, can meet in gas sensor field WO
3the requirement of coating high-specific surface area, is beneficial to coating in the application in gas sensor field, is expected to produce huge society and economic benefit.
With existing WO
3coating and preparation method thereof is compared, and tool of the present invention has the following advantages:
(1) by oxide-doped nanometer WO
3liquid material is directly sent into plasma flame, overcome the shortcoming that nano-powder poor fluidity is difficult for direct spraying, reduced mist projection granulating process, coating particles has nano-scale, and coating is loose porous has larger specific surface area, be beneficial to the high sensitivity advantage on its gas sensor of performance;
(2) by oxide-doped WCl
6solution as precursor, make WO
3and the preparation of coating unites two into one, prepare air-sensitive coating process with tradition and compare, avoided WO
3crystal grain is further grown up, and is expected to make the sensitivity of air-sensitive coating, selectivity and stability to get a promotion.
Therefore, the oxide-doped WO of a kind of ultra-thin porous submicrometer structure provided by the invention
3the preparation method of air-sensitive coating has that cost is low, superior performance and be adapted to the advantages such as industrialization, in industry, especially gas sensor fields such as environmental protection, electronics and catalysis, has good using value and market outlook.
Accompanying drawing explanation
Fig. 1 is the WO of oxide nano-particles doping of the present invention
3the preparation flow figure of air-sensitive coating;
Fig. 2 is the XRD figure spectrum of the air-sensitive coating of the oxide nano-particles doping of preparation in embodiment 1;
Fig. 3 is the surface microscopic topographic figure (a) of the air-sensitive coating of the oxide nano-particles doping of preparation in embodiment 1, and provides the not WO of doping oxide nanoparticle
3the microscopic appearance figure (b) of coating as a comparison;
Fig. 4 is secondary electron figure (a) and the back scattering figure (b) of the air-sensitive coating of the oxide nano-particles doping of preparation in embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, it is pointed out that following examples are intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Embodiment 1:
In the present embodiment, selecting body material is the sheet glass of the about 1mm of thickness, nanometer Al on this matrix
2o
3particle doping WCl
6coat-thickness prepared by liquid material is about 500nm, wherein Al
2o
3with WCl
6mass ratio be 1:20, coating is WO
3the porous surface that crystal grain stacking forms, wherein WO
3grain size range is 10～50nm.The Al of this porous submicrometer structure
2o
3doping WO
3as shown in Figure 1, concrete preparation method is as follows for the preparation flow of coating:
1, first by commercially available WCl
6join in dehydrated alcohol and stir, ultrasonic dispersion 60min joins the surfactant polyethylene of 0.06wt% (PEG600) in deionized water simultaneously, after stirring, is joined WCl
6ethanol solution in, ultrasonic dispersion 40min, obtains WCl
6solid content is 4% solution, and wherein deionized water and dehydrated alcohol 1:1 by volume, then, under the condition of magnetic agitation, is adjusted to 7 with ammoniacal liquor the PH of above-mentioned solution, finally adds a certain amount of nanometer Al
2o
3, magnetic agitation 30min, obtains the liquid phase presoma of plasma spraying;
2, matrix is cleaned for several times successively to 80 ℃ of oven dry with acetone, hydrochloric acid, deionized water;
3, adopt the outer feeding style of plasma spray gun, under constant flow pump effect, a certain amount of liquid material is passed through
nozzle, vertically sends into flame root, and liquid material is dried, calcines, condenses under the high temperature action of plasma flame flow, is deposited on matrix surface, at matrix surface, forms the coating that thickness is about 500nm.Wherein, the spray parameters of controlling plasma spray gun is: electric current 600A, and voltage 55V, spraying liquid material flow 50ml/min, spray distance is 170mm, plasma gun translational speed 300mm/s, coating spraying number of times 10 times.
The coating of above-mentioned preparation is carried out to following Performance Detection:
(1) coating substance phase: utilize X-ray diffractometer (XRD) to detect coating substance phase structure, Fig. 2 is the coating XRD figure spectrum making in the present embodiment, and as seen from the figure, in coating, essential substance is WO
3, illustrate by plasma spraying with liquid feedstock and can obtain stable WO
3coating.Meanwhile, the limitation because XRD detects, does not detect Al
2o
3, may be the nanometer Al of doping
2o
3content is very few or it is by WO
3due to parcel.
(2) coatingsurface pattern: utilize field emission scanning electron microscope (FESEM) to detect coatingsurface microscopic appearance, for improving electron microscopic observation effect, sample surfaces is sprayed to Pt to strengthen its electroconductibility.In Fig. 3, (a) the coatingsurface SEM photo for making in the present embodiment, as seen from the figure, Al
2o
3doping WO
3coating is that uniform particle packing becomes porous surface.Particle size is 10～50nm, (b) for the present embodiment same process under the WO of the not doping oxide nanoparticle prepared
3the pattern of coating, can see that coating also presents loose porous structure, but WO
3grain-size be 70～200nm, much larger than doping coating grain-size.And less grain-size can make coating have high-specific surface area, be beneficial to the gas-sensitive property of performance coating, therefore the coating of doping is more conducive to be applied in gas sensor field.
(3) coatingsurface element: utilize field emission scanning electron microscope (FESEM) back scattering qualitative detection to analyze elemental composition in coating and distribute, in Fig. 4, (a) be the pattern of coating under secondary electron, (b) be back scattering pattern, by (b), can find out Al in doping coating
2o
3distribute comparatively even.
Embodiment 2:
In the present embodiment, matrix is the Al of the about 1mm of thickness
2o
3sheet, this matrix surface WO
3the thickness of coating is about 600nm, and coating is combined with matrix well; Coatingsurface is by WO
3crystal grain is piled up and is formed, and grain size range is at 10～30nm.This porous submicron-scale WO
3the concrete preparation method of coating is as follows:
1, first by commercially available WCl
6join in dehydrated alcohol and stir, ultrasonic dispersion 30min joins the surfactant polyethylene of 0.06wt% 20000 in deionized water simultaneously, after stirring, is joined WCl
6ethanol solution in, ultrasonic dispersion 30min, obtains WCl
6solid content is 4% solution, and wherein deionized water and dehydrated alcohol 1:1 by volume is then adjusted to 7 with ammoniacal liquor the pH of above-mentioned solution under the condition of magnetic agitation, finally adds a certain amount of nanometer Al
2o
3, Al wherein
2o
3with WCl
6mass ratio be 1:10, obtain the liquid phase presoma of plasma spraying;
2, matrix is cleaned for several times with acetone, hydrochloric acid, deionized water successively, to Al
2o
3sheet adopts 60 order corundum sands to carry out surface sand-blasting roughening treatment, and the air pressure that sandblast adopts is 0.5MPa, makes its roughness reach spraying requirement;
3, adopt the outer feeding style of plasma spray gun, under constant flow pump effect, a certain amount of liquid material is passed through
nozzle, vertically sends into flame root, under the high temperature action of plasma flame flow, is dried, calcines, condenses, and is deposited on matrix surface, directly at matrix surface, forms the coating that thickness is about 600nm.Wherein, the spray parameters of controlling plasma spray gun is: electric current 600A, and voltage 55V, spraying liquid material flow 50ml/min, spray distance is 170mm, plasma gun translational speed 300mm/s, coating spraying number of times 15 times.
The coating of above-mentioned preparation is carried out to following Performance Detection:
(1) coating substance phase: utilize X-ray diffractometer (XRD) to detect coating substance phase structure, confirm that in coating, main crystalline phase material is WO
3, illustrate by this technique and can obtain stable WO
3coating.Meanwhile, the limitation because XRD detects, does not detect Al
2o
3, may be the nanometer Al of doping
2o
3content is very few or due to WO
3parcel due to.
(2) coatingsurface microscopic appearance: utilize field emission scanning electron microscope (SEM) to detect coatingsurface microscopic appearance, confirm that coating is that single-size is piled into loose porous surface, and WO
3particle is mainly piled up and is formed with the crystal grain of 10～30nm, shows as vesicular structure, has higher specific surface area, is beneficial to the lifting of coating gas-sensitive.
In contrast, the WO of doping oxide nanoparticle not under our preparation and the present embodiment same process
3coating, observes its pattern, can see that coating also presents loose porous structure, but WO
3grain-size be 80～300nm, much larger than doping coating grain-size.
(3) coatingsurface element: the elemental composition of utilizing field emission scanning electron microscope (FESEM) back scattering qualitative detection to analyze in coating distributes, research is found, Al in doping coating
2o
3distribute comparatively even
Embodiment 3:
In the present embodiment, matrix is the slide glass of the about 1mm of thickness, this matrix surface WO
3the thickness of coating is about 500nm, and coating is combined with matrix well; Coatingsurface is by WO
3crystal grain is piled up and is formed, and grain size range is at 10～40nm.The WO of this porous submicrometer structure
3the concrete preparation method of coating is as follows:
1, first by commercially available WCl
6join in dehydrated alcohol and stir, ultrasonic dispersion 40min joins the tensio-active agent cetyl trimethylammonium bromide of 0.06wt% in deionized water simultaneously, after stirring, is joined WCl
6ethanol solution in, ultrasonic dispersion 40min, obtains WCl
6solid content is 4% solution, and wherein deionized water and dehydrated alcohol 1:1 by volume is then adjusted to 7 with ammoniacal liquor the pH of above-mentioned solution under the condition of magnetic agitation, finally adds a certain amount of nano-TiO
2, TiO wherein
2with WCl
6mass ratio be 1:100, obtain the liquid phase presoma of plasma spraying;
2, matrix is cleaned successively to 60 ℃ of oven dry with acetone, hydrochloric acid, deionized water;
3, adopt the outer feeding style of plasma spray gun, under constant flow pump effect, a certain amount of liquid material is passed through
nozzle, vertically sends into flame root, under the high temperature action of plasma flame flow, is dried, calcines, condenses, and is deposited on matrix surface, directly at matrix surface, forms the coating that thickness is about 500nm.Wherein, the spray parameters of controlling plasma spray gun is: electric current 600A, and voltage 55V, spraying liquid material flow 50ml/min, spray distance is 170mm, plasma gun translational speed 300mm/s, coating spraying number of times 10 times.
The coating of above-mentioned preparation is carried out to following Performance Detection:
1) coating substance phase: utilize X-ray diffractometer (XRD) to detect coating substance phase structure, confirm that in coating, main crystalline phase material is WO
3, illustrate by this technique and can obtain stable WO
3coating.Meanwhile, the limitation because XRD detects, does not detect TiO
2, may be the nano-TiO of doping
2due to content is very few.
(2) coatingsurface microscopic appearance: utilize field emission scanning electron microscope (SEM) to detect coatingsurface microscopic appearance, confirm that coating is that uniform particle packing becomes loose porous surface, and the WO of submicron-scale
3particle is mainly with the WO of 10～40nm
3crystal grain is piled up and is formed, and also shows as vesicular structure, has higher specific surface area, is beneficial to the lifting of coating gas-sensitive.
In contrast, the WO of doping oxide nanoparticle not under our preparation and the present embodiment same process
3coating, observes its pattern, can see that coating also presents loose porous structure, but WO
3grain-size be 70～200nm, much larger than doping coating grain-size.
(3) coatingsurface element: the elemental composition of utilizing field emission scanning electron microscope (FESEM) back scattering qualitative detection to analyze in coating distributes, research is found, TiO in doping coating
2distribute comparatively even.
Embodiment 4:
In the present embodiment, matrix is the silicon chip of scraping of thickness approximately 470 μ m, this matrix surface WO
3the thickness of coating is about 700nm, and coating is combined with matrix well; Coatingsurface is by WO
3crystal grain is piled up and is formed, and grain size range is at 10～30nm.The WO of this porous submicron-scale
3the concrete preparation method of coating is as follows:
1, first by commercially available WCl
6join in dehydrated alcohol and stir, ultrasonic dispersion 50min joins the surfactant polyethylene of 0.06wt% 6000 in deionized water simultaneously, stirs and is joined WCl
6ethanol solution in, ultrasonic dispersion 50min, obtains WCl
6solid content is 4% solution, and wherein deionized water and dehydrated alcohol 1:1 by volume is then adjusted to 7 with ammoniacal liquor the pH of above-mentioned solution under the condition of magnetic agitation, finally adds a certain amount of nano-TiO
2, wherein, TiO
2with WCl
6mass ratio be 1:20, magnetic agitation 40min, obtains the liquid phase presoma of plasma spraying;
2, matrix is cleaned successively to 60 ℃ of oven dry with acetone, hydrochloric acid, deionized water;
3, adopt the outer feeding style of plasma spray gun, under constant flow pump effect, a certain amount of liquid material is passed through
nozzle, vertically sends into flame root, and high temperature action issues biochemical reaction and generates WO
3, under the high temperature action of plasma flame flow, be dried, calcine, condense, be then deposited on matrix surface, at matrix surface, form the WO that thickness is about 700nm
3coating.Wherein, the spray parameters of controlling plasma spray gun is: electric current 600A, and voltage 55V, spraying liquid material flow 50ml/min, spray distance is 170mm, plasma gun translational speed 300mm/s, coating spraying number of times 20 times.
The coating of above-mentioned preparation is carried out to following Performance Detection:
(1) coating substance phase: utilize X-ray diffractometer (XRD) to detect coating substance phase structure, confirm that in coating, main crystalline phase material is WO
3, illustrate by this technique and can obtain stable WO
3coating.Meanwhile, the limitation because XRD detects, does not detect TiO
2, may be the nano-TiO of doping
2due to content is very few.
(2) coatingsurface microscopic appearance: utilize field emission scanning electron microscope (SEM) to detect coatingsurface microscopic appearance, confirm that the particle packing that coating is uniform submicron-scale becomes loose porous surface, and the WO of submicron-scale
3particle is mainly piled up and is formed with the crystal grain of 10～30nm, also shows as vesicular structure, has higher specific surface area, is beneficial to the lifting of coating gas-sensitive.
In contrast, the WO of doping oxide nanoparticle not under our preparation and the present embodiment same process
3coating, observes its pattern, can see that coating also presents loose porous structure, but WO
3grain-size be 80～300nm, much larger than doping coating grain-size.
(3) coatingsurface element: the elemental composition of utilizing field emission scanning electron microscope (FESEM) back scattering qualitative detection to analyze in coating distributes, research is found, TiO in doping coating
2distribute comparatively even.
Embodiment 5:
In the present embodiment, body material is the silicon chip of scraping of thickness approximately 470 μ m, this matrix surface WO
3the thickness of coating is about 1 μ m, and coating is combined with matrix well; Coatingsurface is by WO
3crystal grain is piled up and is formed, WO
3grain size range is at 10～50nm.This porous submicrometer structure WO
3the concrete preparation method of coating is as follows:
1, first by commercially available WCl
6join in dehydrated alcohol and stir, ultrasonic dispersion 60min, the surfactant polyethylene of 0.06wt% 600 and polyethylene glycol 6000 are joined in deionized water, wherein the mass ratio of Polyethylene Glycol-600 and polyethylene glycol 6000 is 1:1 simultaneously, after stirring, is joined WCl
6ethanol solution in, ultrasonic dispersion 60min, obtains WCl
6solid content is 4% solution, and wherein deionized water and dehydrated alcohol 1:1 by volume, then, under the condition of magnetic agitation, is adjusted to 7 with ammoniacal liquor the pH of above-mentioned solution, finally adds a certain amount of TiO
2nanoparticle, wherein, TiO
2with WCl
6mass ratio be 1:10, magnetic agitation 40min, obtains the liquid phase presoma of plasma spraying;
2, matrix is cleaned for several times successively to 80 ℃ of oven dry with acetone, hydrochloric acid, deionized water;
3, adopt the outer feeding style of plasma spray gun, under constant flow pump effect, a certain amount of liquid material is passed through
nozzle, vertically sends into flame root, and liquid material is with flame atomizing pyrolysis, and at matrix surface, forming thickness is the WO of 1 μ m
3coating.Wherein, the spray parameters of plasma spray gun is: electric current 600A, and voltage 55V, spraying liquid material flow 50ml/min, spray distance is 170mm, plasma gun translational speed 300mm/s, coating spraying number of times 30 times.
The coating of above-mentioned preparation is carried out to following Performance Detection:
(1) coating substance phase: utilize X-ray diffractometer (XRD) to detect coating substance phase structure, confirm that in coating, main crystalline phase material is WO
3, illustrate by this technique and can obtain stable WO
3coating.Meanwhile, the limitation because XRD detects, does not detect TiO
2, may be the nano-TiO of doping
2content is very few or by WO
3due to parcel.
(2) coatingsurface microscopic appearance: utilize field emission scanning electron microscope (SEM) to detect coatingsurface microscopic appearance, confirm that the particle packing that coating is uniform submicron-scale becomes loose porous surface, and the WO of submicron-scale
3particle is mainly with the WO of 10～50nm
3crystal grain is piled up and is formed, and also shows as vesicular structure, has higher specific surface area, is beneficial to the lifting of coating gas-sensitive.
In contrast, the WO of doping oxide nanoparticle not under our preparation and the present embodiment same process
3coating, observes its pattern, can see that it also presents loose porous structure, but WO
3grain-size be 80～300nm, much larger than doping coating grain-size.And less grain-size can make coating have high-specific surface area, be beneficial to the gas-sensitive property of performance coating, therefore the coating of doping is more conducive to be applied in gas sensor field.
(3) coatingsurface element: the elemental composition of utilizing field emission scanning electron microscope (FESEM) back scattering qualitative detection to analyze in coating distributes, research is found, TiO in doping coating
2distribute comparatively even.
Claims (9)
1. the WO of oxide nano-particles doping
3the preparation method of air-sensitive coating, is characterized in that, comprises the steps:
WCl with oxide nano-particles doping
6solution is as spraying raw material, through hot-spraying techniques, spraying raw material is spray deposited to matrix, obtains the WO of oxide nano-particles doping
3the grain-size air-sensitive coating that is 10～50nm;
Described oxide nano-particles and WCl
6mass ratio be 1:5～100.
2. the WO that oxide nano-particles according to claim 1 adulterates
3the preparation method of air-sensitive coating, is characterized in that, described oxide nano-particles is aluminium sesquioxide nanoparticle or titanium dioxide nano-particle, and the particle diameter of aluminium sesquioxide nanoparticle is 20～60nm, and the particle diameter of titanium dioxide nano-particle is 5～30nm.
3. the WO that oxide nano-particles according to claim 1 and 2 adulterates
3the preparation method of air-sensitive coating, is characterized in that, the preparation process of described spraying raw material is:
First by WCl
6join in dehydrated alcohol, fully, after reaction, add water and tensio-active agent, and regulate pH value to 7～8 with ammoniacal liquor, then add oxide nano-particles, after mixing, obtain spraying raw material;
WCl in described spraying raw material
6quality percentage composition be 4～10%, the quality percentage composition of tensio-active agent is 0.06～0.15%, the volume ratio of water and dehydrated alcohol is 1:1～4.
4. the WO that oxide nano-particles according to claim 3 adulterates
3the preparation method of air-sensitive coating, is characterized in that, described tensio-active agent is at least one in polyoxyethylene glycol, cetyl trimethylammonium bromide, ammonium polyacrylate.
5. the WO that oxide nano-particles according to claim 4 adulterates
3the preparation method of air-sensitive coating, is characterized in that, WCl in described spraying raw material
6quality percentage composition be 4%, the quality percentage composition of tensio-active agent is 0.06%, the volume ratio of water and dehydrated alcohol is 1:1;
Described oxide nano-particles and WCl
6mass ratio be 1:10～100;
Described tensio-active agent is polyoxyethylene glycol or cetyl trimethylammonium bromide.
6. the WO that oxide nano-particles according to claim 1 adulterates
3the preparation method of air-sensitive coating, it is characterized in that, described thermospray is plasma spraying, concrete technology parameter is: the electric current of plasma spraying is 550～650A, voltage is 45～60V, and spraying raw material flow is 30～80ml/min, and spray distance is 140～200mm, plasma gun translational speed is 300～600mm/s, and coating spraying pass is 10～30 times.
7. the WO that oxide nano-particles according to claim 6 adulterates
3the preparation method of air-sensitive coating, is characterized in that, the electric current of plasma spraying is 600A, and voltage is 55V, and spraying raw material flow is 50ml/min, and spray distance is 170mm, and plasma gun translational speed is 300mm/s, and coating spraying pass is 15～30 times.
8. the WO that oxide nano-particles according to claim 1 adulterates
3the preparation method of air-sensitive coating, is characterized in that, described matrix is aluminum oxide, No. 45 steel, 304 stainless steels, polished silicon slice or slide glasss.
9. the WO of the oxide nano-particles doping that prepared by method according to claim 1
3air-sensitive coating, is characterized in that, WO in air-sensitive coating
3grain-size be 10～50nm.
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| CN108970601A (en) * | 2018-07-09 | 2018-12-11 | 中国科学院宁波材料技术与工程研究所 | A kind of photocatalysis coating and its preparation method and application with Zinc oxide/titanium dioxide heterojunction structure |
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